SE438161B - RELATIVE PARTICULAR DETERGENT SOFTENING COMPOSITION AND PROCEDURE FOR ITS PREPARATION - Google Patents

Description

7113167-o mixed with sodium bicarbonate, sodium carbonate, sodium bicarbonate, pentasodium tripolyphosphate, tetrasodium pyrophosphate, sodium silicate, borax, the corresponding potassium salts, and mixtures thereof, which particles contain a non-liquid liquid or and on the surfaces thereof and coated with calcium ion exchange zeolite particles having a final particle diameter in the range of 0.005 - 20 .mu.m adhering to the nonionic detergent. the surfaces of the gene washing agent salt particles, and a waxy quaternary ammonium compound as a plasticizer, which is located externally on or within said particles, said zeolite having the following chemical formula: (m 2 O) (Al 2 O 3) y (sio 2) z> _ <w H 2 O where M ~ is sodium or potassium, y is 0.8 - 1.2, z is 1.5 - 3.8 and W is the water content of about 1.5 - 36% by weight of said zeolite, and the weight percent of said builder salt, said nonionic detergent, said zeolite and said plasticizer are in the range of 20 - 40%, 12 - 30%, 30 - 60% and 4 - 12% respectively; The products of the present invention are excellent strong or high performance detergent fabric softener compositions having suitably high bulk densities to enable small volumes of the compositions, for example 50 to 150 cm 3, to be used for an average wash in an automatic washing machine (which has a cylinder volume). of about 30 - 65 liters and washes a 4 kg batch of soiled laundry, etc). Smaller packages can thus be used for similar effective quantities of the detergent plasticizer composition and storage spaces can be saved in the store and at home. Of course, it is also easier to handle the smaller packages and to pour them out, which means more convenient use and less spillage.

The core particles or base particles into and onto which nonionic detergent is added may be of any suitable builder salts which are sufficiently sorptive for the nonionic detergent, when in the liquid state. Normally, it is desirable that the builder salt particles have rounded forms, most preferably spherical, with openings or channels through the particles to the inner portions thereof, which allow sorption of at least 10%, preferably 20% and most preferably 30% or more, of nonionic detergent (% by weight) into the detergent salt particles. Suitable detergent salts which may be used include a preferred mixture of sodium carbonate and sodium bicarbonate (including Wegscheider's salt), as will be described in more detail, sodium carbonate, sodium bicarbonate, pentasodium tripolyphosphate, tetrasodium pyrophthalophenate l: 1.6 - 1: 3) and borax. These products, which can be spray dried, agglomerated or prepared by the appropriate methods of others, preferably have particle sizes similar to those of the preferred carbonate-bicarbonate mixture to be described below. Mixtures of different builder salt contents can of course be used as is the case with mixtures of the various other components of the invented compositions.

In addition to the sodium salts, other alkali metal salts, principally potassium salts, may be used, but these are not normally preferred.

Instead of a portion of the inorganic builder salt, organic builder salts may be used, such as sodium citrate, trisodium nitrolotriacetate, CMOS (sodium carboxymethyloxy succinate), sodium gluconate and sodium EDTA. However, the total content of such organic builder salts is usually only a minor proportion of the total content of builder material, preferably it is less than 25% thereof. Some of the builder salt can also be replaced by sodium sulfate or other compatible filler, but even in this case this is usually included in only a minor proportion and is preferably less than 25% of the total content of builder material plus filler content. * The preferred mixture of alkali metal carbonate and alkali metal bicarbonate is very preferably a mixture thereof where both types of compounds are contained in the same individual grain or particles. For the purpose of the present invention, these particles should desirably have sizes in the range 0.149 - 0.84 mm, preferably 0.250 - 0.59 mm and most preferably about 0.42 mm. Larger particles, up to about 2.38 mm, can be used provided that the particle size of the resulting final product is within the desired range. In some cases, efforts are made to prevent any agglomeration or significant particle size growth from occurring during the absorption of nonionic detergent or otherwise as the final particle sizes will usually be too large. When sizes smaller than those falling within the desired range are used, an unacceptable pasty product is sometimes formed, rather than individual free-flowing grains or beads.

The alkali metal (sodium or potassium preferred) carbonates and bicarbonates, most preferably the sodium salts, are substantially anhydrous in preferred embodiments of the invention, but partially dehydrated detergent salts of this type may be tolerated. Normally the moisture contents are less than 9%, preferably less than 7%. The weight ratio of alkali metal carbonate to alkali metal bicarbonate is generally in the range of 1:10 ~ 10: 1, preferably in the range of 1: 5 - 1: 1, more preferably in the range of 1: 3 - 1: 1 and most preferably about 1: 2. The mixed product is preferably made by a method which results in a substantial content, e.g. 10 - 100%, of Wegscheider's salt, the remainder being sodium bicarbonate. Such a product has excellent sorptive ability for liquid nonionic de- ... 'fl v ~ »n --______._.....__ i ____._....._, _.,. .-.__., _, _ 7713167-0 tergent and can be easily transferred to a suitable base for a powder-like coating or coating of zeolite scrubbing material. One method of making a carbonate-bicarbonate blend product which has been used successfully is disclosed in U.S. Patent 3,944,500, which is incorporated herein by reference. A useful mixed carbonate-bicarbonate product of the type described can be obtained from Allied Chemical Corporation under the trademark Snowlite Go Although the method of said patent is a preferred one, the mixed carbonate-bicarbonate grains can be manufactured by other techniques.

Instead of the carbonate and bicarbonate, which are intimately combined in single grains, according to one aspect of the present invention, separate batches of carbonate and bicarbonate may be used, preferably of the same sizes and proportions as for the products described above, provided that the are sufficiently sorptive to take up the nonionic detergent in sufficient quantity to form the desired end products. It is also possible to use more finely divided carbonate and bicarbonate powders, such as those having particle sizes below 0.149 mm, e.g. 0.053 - 0.88 mm, and agglomerate these, either separately or in admixture, being careful to preserve the porosity of the product by using only small amounts of a binder, such as starch or other agglomerating agent. Wegscheider's salt can also be added to such products.

The emollient compounds that can be used to soften laundry and help make clothes wrinkle resistant and free of static electricity include a wide variety of compounds that have essential parts of their molecules positively charged. These compounds generally include hydrophobic groups as parts of the positively charged moieties and often these groups are relatively long chain radicals, such as higher hydrocarbyls or alkyls.

Although amines, imidazolines, pyridines, guanidines and salts and derivatives thereof are useful, especially if they contain relatively long chain hydrophobic groups, the most preferred plasticizers are usually quaternary ammonium compounds containing a 'rocm Quinn' or two long chain hydrophobic groups and two or three short chain groups, with a solubilizing cation or a salt-forming group, usually either halide, sulphate, acetate, hydroxide or other inorganic or organic solubilizing mono- or dibasic radical. A variety of cationic compounds useful in the present invention are also described in U.S. Patents 3,227,614 and 3,442,692.

In the quaternary ammonium compounds and salts, the long chain substituents on the nitrogen are preferably higher alkyl groups having 12 to 18 carbon atoms, more preferably 16 to 18 carbon atoms and most preferably stearyl, and the shorter hydrophobic radicals are alkyls having 1 to 4 carbon atoms, preferably 1-2 carbon atoms and most preferably methyl. Similar long chain substituents are found on the imidazolines and imidazoles, pyridines and piperidines, guanidines and amines. Specific examples of preferred cationic conditioning agents used in accordance with the present invention include dimethyl distearylammonium chloride; trimethylstearylammonium bromide; cetyltrimethylammonium chloride; di-higher alkyldimethylammonium chloride wherein the higher alkyl is obtained from hydrogenated tallow alcohols; cetylpyridinium chloride; higher-alkyl dimethylbenzylammonium chloride; diisobutylphenoxyethoxyethyl dimethylbenzylammonium chloride; * and laurylisoquinolinium bromide. Although these are preferred compounds, the higher alkylamines, and other cationic conditioning agents known to be useful in softening various fabrics and fibers and making them wrinkle resistant or static free may also be used instead. Such compounds are strongly substantive on textiles, especially those of cotton or cellulosic material and synthetic organic fibers. The described emollient compounds comprising higher alkyl groups are also usually waxy or pasty solids and may be softened or melted at elevated temperatures so that they may be used to coat the base particles of the present invention. These coatings or coatings may be performed by mixing comparatively soft particles of emollient compound with materials to which these particles are to be adhered, such as carbon-bicarbonate-nonionic-detergent-zeolite particles or the emollient can be melted and sprayed on the base particles or it can be mixed with nonionic detergent and commonly sprayed on such particles. In the present products, largely due to the use of nonionic detergent instead of anionic detergent with which cationic plasticizers often react, the emollient compound will retain its effectiveness in use.

The nonionic detergents include those described in detail in McCutcheon's "Detergents and Emulsifiers", 1973 Annual and in "Surface Active Agents", Volume II by Schwartz, Perry and Berch (Interscience Publishers, l958), to which books are hereby incorporated by reference. These nonionic detergents are usually pasty or waxy solids at room temperature (at 200 ° C) which are either sufficiently water soluble to dissolve directly in water or will melt rapidly at the temperature of the wash water, such as when this temperature is above 40 ° C. The nonionic detergents used are normally those which are liquid or pasty at room temperature, but preference is given to the normally pasty or semi-solid products, as these are less likely to produce a sticky product with poor dispersibility properties and sensitive to clumping or solidification during storage. They are also less likely to drip and release their "mounts" on the zeolites. Nevertheless, liquid nonionic detergents can normally be used and nonionic detergents used are transferable to liquid form so that they can be sprayed at reasonable temperatures, such as temperatures below 45 °, 500 or 600 ° C. Typical useful nonionic detergents are poly- (lower -alkenoxy) derivatives which are usually prepared by condensation of lower (2-4 carbon atoms) -alkylene oxide, e.g. ethylene oxide, propylene oxide (with sufficient ethylene oxide to provide a water-soluble product), with a compound having a hydrophobic hydrocarbon chain and containing one or more active hydrogen atoms, such as higher alkylphenols, higher fatty acids, higher fat mercaptans, higher fatty acids fatty amines and higher-fat polyols and alcohols, e.g. fatty alcohols having 8 to 20 or w1? c) () ïšvc2xJ1åIÄrIä {7713167-0 10 - 18 carbon atoms in an alkyl chain and alkoxylated with an average of about 3 - 30, preferably 3 - 15 or 6 - 12 lower alkylene oxide units. Preferred nonionic surfactants are those represented by the formula RO (C 2 H 4 O) n H, wherein R is the residue of a linear saturated primary alcohol (an alkyl) having 10 or 12 to 18 carbon atoms and n is an integer from 3 or 6 to 15 Typical commercial nonionic surfactants suitable for use in the invention include Neodol 45-11l, which is an ethoxylation product (having on average about 11l ethylene oxide units) of a fatty alcohol having a 14-15 chain. carbon atoms (average) (manufactured by Shell Chemical Company); Neodol 25-7, fatty alcohol with a chain of 12-15 carbon atoms where the fatty alcohol has been ethoxylated with an average of 7 ethylene oxide units; and Alfonic 1618-65, which is an alkanol having 16 to 18 carbon atoms ethoxylated with an average of 10 to 11 ethylene oxide units (Continental Oil Co.).

Also useful are the Igepal materials from GAF Co., Inc. These materials are usually the polyethoxylated (3 - 30 ethylene oxide units) intermediate alkyl phenols (where the alkyl has 6 to 10 carbon atoms), such as the Igepal materials CA-630, CA 730 and CO-630. The Pluronic® 9-(material (manufactured by BASF-Wyandotte), such as Pluronic F-68 and Pluronic F-127, which are condensates of ethylene oxide with hydrophobic bases formed by condensing propylene oxide with propylene glycol, which usually have molecular weights in the range 5,000 - 25,000, can also be used as is the case with the various Tween É) materials (products from ICI America), which are polyethoxylene sorbitan higher fatty acid (1-2-18 carbon atoms) esters, such as those contains solubilizing amounts of ethylene oxide therein. A variety of other nonionic detergents described in the above books may also be used, but preferably the proportion of nonionic detergent or surfactant included, when other than the higher fatty alcohol polyoxyethylene ethanols are used, is less so and said amount is rare. more than 50% and preferably not more than 25% of the total nonionic detergent content.

In the above description, "higher", such as in higher alkyl, higher fat, etc., means from 8 to 20, preferably from 10 or 12 L to 18 carbon atoms. The zeolites which can be used in the practice of the present invention include the crystalline, amorphous and mixed crystalline-amorphous zeolites of both natural and synthetic origin, which have satisfactorily fast and sufficiently effective effects in counteracting hardness-forming ions. such as calcium ions, in the wash water. These materials are preferably capable of reacting rapidly enough with hardening cations, such as calcium, magnesium, iron and the like or any of them, to soften the wash water before adverse reactions of such hardening ions take place with other components of the synthetic organic the detergent composition. The zeolites used can be characterized in such a way that they have a high ion exchange capacity for calcium ion, which normally ranges from about 200 to 400 or more milligram equivalents of calcium carbonate hardness per gram of the aluminosilicate, preferably 250 - 350 mg / eq./ grams and a hardness depleting rate of the residual hardness of 0.02 - 0.05 mg CaCO3 / liter for 1 minute, preferably 0.02 - 0.03 mg / liter, and less than 0.01 mg / liter for 10 minutes. minutes, calculated in all cases on the basis of an anhydrous zeolite.

Although other ion exchange zeolites may also be used, the finely divided synthetic zeolite builder material used in the practice of the present invention is of the formula (Nazo) x- (Aizoyy- (S102) Zw H 2 O wherein x is 1, y is from 0.8 to 1 , 2, preferably about 1, z is from 1.5 to 3.5, preferably 2 to 3 or about 2 and wp from 0 to 9, preferably 2.5 to 6.

The water-soluble crystalline aluminosilicates used are often characterized in that they have a network of pores which are uniformly sized in the range of about 3 to 10 Angstroms, which pores are often about 4 Angstroms (normally), which size is determined on a peculiar way through the unitary structure of zeolite crystal- - ...-.._. _. ? 713 @ ß7 + o 10 len. Zeolites containing 2 or more such networks with different pore sizes can of course also be used satisfactorily as is the case with mixtures of such crystalline materials with each other and with amorphous materials, etc.

The zeolite should be a monovalent cation exchange zeolite, i.e. it should be an aluminum silicate of a monovalent cation such as sodium, potassium, lithium (when feasible) or other alkali metal, ammonium or hydrogen. The monovalent cation of the zeolite molecular sieve is preferably an alkali metal cation, especially sodium or potassium, and most preferably it is sodium but a variety of other types are also useful.

Crystalline types of zeolites that can be used as good ion exchangers in the invention, at least in part, include zeolites with the following crystal structure groups: A, X, Y, L, mordenite and erionite, of which types A, X and Y are preferred. Mixtures of such molecular sieve zeolites may also be useful, especially when type A zeolite is included. These crystalline types of zeolites are well known in the art and are described in more detail in the book "Zeolite Molecular Sieves" by Donald W. Breck, published in 1974 by John Wiley & Sons. Typical commercially available zeolites of the above structure types are listed in Table 9.6 on the pages. 747 - 749 of the said book, to which table is hereby referred.

The zeolite used in the invention is preferably synthetic and it is also preferred that it be of type A or similar structure as specifically described on page 133 of the latter book.

Good results have been obtained when a type 4A molecular sieve zeolite is used, wherein the monovalent cation of the zeolite is sodium and the pore size of the zeolite is about 4 Angstroms. These zeolite molecular sieves are described in U.S. Patent 2,882,243, which discloses them as Zeolite A. Molecular sieve zeolites can be prepared in either a dehydrated or calcined form containing from about 0 or about 1.5% to about 3% moisture. or in a hydrated or water-laden form containing additional bound water in an amount from about 4% up to about 36% of the total weight of the zeolite depending on the type of zeolite used. The aqueous hydrated form of the molecular sieve zeolite (preferably about 15-70% hydrated) is preferred in the practice of the present invention when this crystalline product is used. The production of such crystals is well known in the art. In the preparation of, for example, Zeolite A, as disclosed in the above-mentioned patents, the hydrated zeolite crystals formed in crystallization medium (such as an aqueous amorphous sodium aluminum silicate gel) were used, without the high temperature dehydration (calcination to 3% or lower water content ) normally practiced in the preparation of such crystals for use as catalysts, e.g. cracking catalysts. The crystalline zeolite can be recovered in either fully hydrated or partially hydrated form by filtering the crystals from crystallization medium and drying the crystals in ambient temperature air so that their water contents are in the range of from about 5 to 30% moisture, preferably about 10 - 25%, such as 17 - 22%. However, the moisture content of the molecular sieve zeolite used can be much lower as previously described.

The zeolites used in the invention should also generally be substantially free of adsorbed gases, such as carbon dioxide, as such gas-containing zeolites may form undesired foaming when the zeolite-containing detergent is contacted with water. Sometimes, however, foaming is tolerated and it may sometimes be desirable.

The zeolite should preferably be in a atomized state with final particle diameters up to 20 microns, e.g. 0.005 or 0.01 to 20 microns, preferably 0.01 to 15 microns and particularly preferably 0.01 to 8 microns in average particle size, e.g. 3 - '° **' - '"' åv-H *" A - ~ '7- -------: - .. ~ ....., __...._... _........ w._ __ # .., __. r _> _._. w., -... ~, ..._._ ,,,,, _ ,, _ ,, P "" '“" "" "' 'Peer Qszxnw 7713167-0 12 7 or 12 microns, if in the case of crystalline zeolites, and 0.01 - 0.1 microns, eg 0.01 - 0.05 microns in the case of amorphous zeolites. Although the final particle sizes are much larger, the zeolite particles are usually of sizes falling in the range of 0.037 - 0.149 mm, preferably 0.044 - 0.105 mm. Zeolites of smaller sizes will often be remarkably dusty and those of larger sizes cannot adequately and satisfactorily cover or coat the carbonate-bicarbonate base particles.

Although the crystalline synthetic zeolites are more common and better known, amorphous zeolites can be used instead and are often superior to the crystalline materials in a variety of significant properties, as will be described, as is the case with mixed crystalline-amorphous materials and mixtures of the different types of zeolites described. The particle sizes and pore sizes of these materials may be the same as previously described, but variations from the stated ranges may be made as described provided that the materials function satisfactorily as washers and do not remarkably whiten colored materials too much with which materials are treated in aqueous medium.

A variety of suitable crystalline molecular sieve zeolites are described in DE-A * 25199815, DE-A 2538679, DE-A-2656251 and DE-A-2656009, to which reference is hereby made with respect to the zeolites and other materials used therein. present invention. A number of different other such compounds are described in the Swedish patent applications sE 74 oazsv-A and sE 77 14 49s-A, to which reference is hereby also made. Other useful such molecular silzeolites are disclosed in German Patents 2,412,837 and 2,412,839 and in Austrian Patent Applications A 4484/73, A 4642/73, A 4666/73, A 4717/73, A 4750/73, A- 4767/73, .A 4787/73, A 4788/73, A 4816/73 and A 4888/73, to which reference is also made. Methods for preparing amorphous and mixed amorphous crystalline aluminosilicate materials as ion exchange zeolites are described in U.S. Patent Application filed July 12, 1974, entitled "Detergent Builder Composition" (Inventor Burton H.

Gedge, III and Bryan L. Madison). Detergent compositions containing such amorphous materials are described in an application filed by John Michael Corkill and Bryan L. Madison on July 18, 1974, and detergent compositions containing mixed amorphous crystalline aluminosilicate as a builder are described in an application filed by the same inventor. July 12, 1974. A preferred ion exchange zeolite is the amorphous zeolite of the formula M2O-Al2O3 '(SiO2) zw H2O disclosed in Belgian Patent 835,351 wherein z is from 2.0 to 3.8 and w is from 2.5 to 6, especially when M is sodium. In order to avoid extensive enumeration of such materials, methods for their preparation and uses, etc. reference is made only to the said patent. A variety of auxiliaries or additives, both functional and aesthetic, may be incorporated into the present compositions, such as bleaching agents, e.g. sodium perborate; paint materials, e.g. pigments, dyes; fluorescent bleach, e.g. stilbene whitening agents; foam stabilizers, e.g. alkanolamides such as lauric acid myristic acid diethanolamide; enzymes, e.g. proteases; skin protective and skin conditioning agents, such as low molecular weight water-soluble proteins obtained by hydrolysis of proteinaceous materials, such as animal hair, hides, gelatin, collagen; defoamers, e.g. silicones; bactericides, e.g. hexachlorophene; and perfumes. These additives and any additional detergent builders are usually mixed with the other components at a particular step in the manufacturing process which is most suitable, which usually depends on the nature of the additive and its physical condition. Particularly desirable are such additives which help to stabilize the additive or other components of the product and / or which increase the ability of the carbonate-bicarbonate mixture to absorb nonionic detergent. These additives can thus be sprayed on the base particles together with the nonionic detergent, can be mixed with the zeolite and applied together with the base particles treated with the nonionic detergent or can be added to such zeolite coated particles, either together with the plasticizer or after the additive of the plasticizer. Normally, it is preferred that only nonionic detergents be used (with the exception of the plasticizer which may be considered to have cationic detergent properties), but sometimes nonionic detergents may be supplemented with an anionic organic detergent, an amphoteric organic detergent or a mixture thereof. However, when these materials are used, they are normally in smaller proportions, preferably less than 25% of the total nonionic detergent and such a detergent (s) and more preferably less than 10% thereof and are so located in the product and so on. incorporated in it that reactions between the emollient and such detergent or detergents which may lead to remarks are reduced to a minimum. Thus, when a cationic plasticizer is added afterwards, it is preferred to spray an anionic and amphoteric detergent (s) into the base particles on and in it together with the nonionic detergent. When the cationic plasticizer is sprayed on the base particles together with the nonionic detergent or separately therefrom, it is preferred to similarly incorporate an anionic and amphoteric detergent (s) onto the surfaces of the zeolite coated grains or they may optionally be mixed with the zeolite and applied on the particles treated with cationic plasticizer and nonionic detergent. Among the anionic detergents which are useful are the sulfates and sulfonates of lipophilic moieties, especially those containing chains having a larger number of carbon atoms, such as those having 8 to 20 or 10 to 18 carbon atoms. Included among these compounds are the linear higher alkyl benzene sulfonates, olefin sulfonates, paraffin sulfonates, fatty acid soaps, higher fatty alcohol sulfates, higher fatty acid monoglyceride sulfates, the sulfated condensation products of ethylene oxide (3 to 30 molar fatty alcohols) the fatty acid esters of isethionic acid and other known anionic detergents, as also mentioned in the previously cited literature references. Most of these products are normally in solid form, usually as alkali metal salts, e.g. sodium, and can be spray-dried together with standard detergent salts. The spray dried particles, including such builder salts, can be used as cores or base particles in the present invention. Agglomeration techniques, size reductions, tabletings and other methods can be used to prepare such intermediates of sizes similar to those of the carbonate-bicarbonate particles. A few examples of suitable anionic detergents include sodium linear tridecylbenzene sulfonate, sodium coconut monoglyceride sulfate, sodium lauryl sulfate and sodium paraffin and olefin sulfonates, each having an average of about 16 carbon atoms. Amphoteric compounds, such as the sodium salt of Miranol C2M and Deriphat® D151, can also be used in the present detergents. Like the anionic detergents, the amphoteric detergents can be spray dried or otherwise co-prepared with a detergent composition or can be dispersed in the liquid nonionic detergent or otherwise suitably mixed with other powders during the manufacture of the present products. Although both anionic and amphoteric detergents may be included in the products of the present invention, it is highly preferred that the only cleaning component, other than the cationic plasticizer, be a nonionic detergent or a mixture thereof.

The proportions of the core or base particles (preferably carbonate-bicarbonate), nonionic detergent, zeolite and plasticizer should be selected to obtain the desired free-flowing detergent plasticizer-containing particles having satisfactory high bulk density, when manufactured by the method of manufacture. - In the present invention. These proportions are 20-40% of core or baeparriklarnejló or 12 to 30 a nenjoniele derergenr, '30 - 60% zeolite and 4 - 12 s_ plasticizers, with preferred ranges being 23 - 33%, 13 - 23_%, 40 - 52% and 5 "- 10% respectively.

The bulk density of the product is at least 0.6 g / cm 3 and is preferably in the range 0.75 - 0.95 g / cm 3 and most preferably it is in the range 0.8 - 0.9 g / cm 3. The particle sizes of the product are usually in the range 0.42 - 4.76 mm, preferably 1.68 - 4.76 mm and most preferably the particle sizes are about 2.38 or 3.36 mm. The particle sizes of the starting material carbonate-bicarbonate or other base particles are, before any treatment, usually in the range from around 0.149 - 0.84 mm, preferably 0.250 - 0.59 mm and are most preferably around 0.42 mm. However, finer carbonate and bicarbonate powders and other builder materials can be used initially and can be agglomerated up to the mentioned sizes. The materials within the stated millimeter ranges are generally a mixture of particles of different sizes within these ranges (this also applies to the various other particulate materials described here).

In the preparation of the carbonate-bicarbonate particles consisting of the preferred starting mixture, one can use the method set forth in U.S. Patent 3,944,500 and the product obtained by this method is preferably used and is identified by the trademark Snowlite, which can be obtained from Allied Chemical Corporation. A typical analysis of Snowlite I shows that it consists of 35% Na2CO3, _58.5% NaHCO3 and 6.5% water, while an analysis of another such product, Snowlite II, gives the values 30.0, 66.5% and 3.5%. Sieve analyzes of these two products (percent on sieve Nos. 10, 40, 60 and 100 according to US Standard) give the following results 0.2, 67.6, 96.9, 99.0 and 0.7, 60, respectively. 7, 90.7 and 97.0. The bulk densities (g / cm3) are 0.51 and 0.48 (packed) and 0.42 and 0.38 (unpacked), respectively. The brittleness is particularly low for Snowlite I (2.5% in Allied Chemical Corp. test Na 17-35) and this product is preferred. Low brittleness and particle strength are also important for other types of base particles that can be used, to prevent them from pulverizing to a greater extent and forming pastes, instead of individual coated particles, when nonionic detergent is added to them. In some cases, other components of the finished product may be incorporated into the mixture of bicarbonate and Wegscheider's salt (sesquicarbonate may also be included), which are prepared by the method of the said patent, provided that they are stable and not harmful to reaction. interferes with or interferes with the production of the carbonate-bicarbonate product. Normally the carbonate-bicarbonate particles contain at least 60%, preferably 70% and more preferably 70-85% or more carbonate and bicarbonate, when such other additives are included, such as 10-20% sodium silicate and / or 0.1-5% fluorescent white. - medium, sometimes also with 5 - 15% water.

The free-flowing particulate detergent plasticizer composition of the present invention can be prepared by any of a variety of methods. In such a method, the described sodium carbonate-sodium bicarbonate particles or other builder particles are mixed with nonionic detergent in liquid form, which detergent is preferably applied by spraying, but it can also in some cases be added as a stream. The detergent penetrates or penetrates the carbonate-bicarbonate particles, but also covers or coats the surfaces of these particles so that the subsequently applied zeolite adheres or adheres to them. It is important to apply a sufficient amount of nonionic detergent so that, in addition to the amount absorbed into the interior of the detergent particles, a certain amount will be left on the particle surfaces. During mixing after the addition of nonionic detergent, the particles resemble wet sand and have a fluffy or waxy appearance. The nonionic detergent is normally liquid, pasty or semi-solid and is preferably pasty or semi-solid to minimize any tendency of the product to become sticky or clumpy during storage, although liquid nonionic detergents may normally also be 'Poon QUALITY 7713167-0 18. be used satisfactorily. After coating with the coating of the base particles with nonionic detergent, these particles are mixed with zeolite powder which will then adhere or adhere to the nonionic detergent on the particle surfaces. The particles produced are mainly spherical and have sizes in the range 0.42 - 4.76 mm. In this embodiment of the manufacturing method, the plasticizer, usually in the form of rather small granules, flakes, beads or powder particles, is mixed with the non-ionic-detergent-zeolite base granules. The plasticizer is normally a waxy or fluffy low melting solid with particle sizes in the range of 160 - 80 mesh, corresponding to about 0.095 - 0.177 mm, these particle sizes preferably being about 0.149 mm. It will be retained physically and / or electrostatically on the surfaces of the zeolite-coated particles. The proportions of the materials used, the mixing times, the temperatures and the mixing techniques used are of course such that the product produced will be of the desired, previously described composition and have the desired properties.

The initial spraying or other mixing of nonionic detergent with the carbonate-bicarbonate particles or other builder particles is normally performed with the particles at about room temperature (20-25 ° C), but the temperature may vary over the range of 10 to 40 or 500 ° C. C. The spraying and mixing can take as little as 1 - 5 minutes and the mixing can be continued after complete spraying for a period of 0 - 10 minutes, preferably 1 - 5 minutes. The higher-fat alcohol-polyethylene oxide condensation product sprayed on the surfaces of the moving grains is usually liquid or heated to an elevated temperature so that it is liquid and sprayed on the moving surfaces or otherwise applied to them so that it is distributed over them and promotes the absorption of the liquid into the porous particles. In addition, some agglomeration may be obtained during the initial mixing, apparently due to the adhesion or cohesion between some of the finer particles included which have "excess" - --_--- - - e - -f --_ ï-- ~ - »- - --_-___._.-._-.«. .__-..._.__--. F ...-_ .., ___ ,,, .. '77103167- 0 "19 amounts of liquid nonionic detergent on the surfaces thereof. During such agglomeration, these particles can be increased in size to sizes approximately within the range of the final product, although the subsequent adhesion of zeolite particles further increases the particle sizes slightly. The nonionic detergent on the moving particles is preferably carried out in a rotating drum or tube which is inclined at a small angle, such as 5 to 15 °. The rotational speed may be any suitable one, such as 5 to 50 rpm. the nonionic detergent is normally made to form fine droplets of this detergent, such as those which have diameters in the range of 40 - 200 microns, preferably 50 - 100 microns, but other suitable sizes of the sprayed droplets may also be formed and in some cases the nonionic detergent may be mixed with the detergent particles after it has been dropped or poured onto the moving surfaces thereof. In some cases, a higher speed high energy mixer, such as a Lodige mixer operating at a comparatively low speed, or a double jacketed mixer or mixer of a similar type, may be used to prevent excessive agglomeration. of particles caused by the addition of the larger droplets or streams of nonionic detergent. As previously stated, although not preferred, sorptive carbonate-bicarbonate particles could be prepared by methods other than those described herein, obtaining products with more angular edges, but it is highly desirable that the particles be sprinkles and therefore they are most preferably slightly rounded.

After the absorption of the nonionic detergent is completed, the zeolite powder is mixed with the product, usually for a period of 1-10 minutes, preferably about 5 minutes, and held on the particles, forming free-flowing particles of particle sizes in the range 0.42. - 4.76 mm. At this stage, the product usually has a moisture content of 2-20%, preferably 5-15%, including hydration water. The plasticizer, in the form and of the particle sizes previously mentioned, is then "dusted" on the surfaces of the particles and for a period of 1-10 minutes, preferably about 5 minutes, it will adhere or stick to Due to the relatively small proportion of cationic plasticizer used, the particle sizes do not increase much and the plasticizer particles are adhered to the detergent salt-nonionic detergent zeolite particles sufficiently to make it a stable, non-segregating and dust-free final product. As previously mentioned, a variety of additives may be incorporated into the product by mixing with appropriate components or they may be added to the product during appropriate process steps during the production of the free-flowing grains or after such preparation is substantially complete. excluding water, rarely exceeds 20% of the product and is normally less than 10 %. If a perborate bleach is used, the percentage thereof can of course be increased to an effective bleaching amount, which can be as high as 30% of the product, it being normal for the proportions of the other important components to be reduced proportionally accordingly. The perborate can be mixed with the carbonate-bicarbonate mixture or it can be added afterwards to the mixture treated with nonionic detergent or to the finished product. Dyes, perfumes and other additives may be mixed with the various components and mixtures during manufacture or after completion.

In modifications of the manufacturing method, which give compositions with the same formulations, but with further improved properties, the cationic plasticizer is melted and applied together with the nonionic detergent at an elevated temperature at which they are both liquid. Alternatively, the plasticizer and the nonionic detergent are applied sequentially to the base particles. In such cases, the particles are usually kept at a high enough temperature so that the liquids do not solidify prematurely, which could prevent further sorption of these materials. When liquid quaternary plasticizer is first applied, - »-. .. _, ___._ ...__ .i _ ___, _ 7713167-0 21 before the nonionic detergent, it tends to penetrate or penetrate into the interior of the base particles so that when the nonionic detergent is added, although some of the it will penetrate into the interior of the particles, a greater proportion thereof than the proportion of the plasticizer will be present on the surfaces of the materials, where it will adhere to the subsequently applied zeolite powder.

In further modifications of the process of the invention, a portion of the nonionic detergent and zeolite is left out and used to perform repeated coating or coating of the product. From about 5 to 50%, preferably about 10 to 30% of the nonionic detergent and the zeolite can thus be applied afterwards to the product, first the nonionic detergent and then the zeolite, thereby forming an additional protective shell around the product and enabling that more nonionic detergent can be incorporated than would otherwise be possible while still obtaining a free-flowing particulate detergent plasticizer mixture. Normally, as many as six coating operations can be performed, but it is preferred that these be limited to three (two repeated coatings or coatings). The products of the present invention have significant advantages over other detergent plasticizer compositions. They can be manufactured as either phosphate-containing, low-phosphate-containing or phosphate-free compositions. The phosphate-free compositions have satisfactory washing properties with respect to varying soils normally found in household laundry and yet comply with the statutory provisions limiting the use of phosphates in detergents. The products produced can therefore be marketed in many countries and there is no need for a large number of different preparations and restrictions in special transports of detergent compositions to certain areas of the country. The satisfactory cleaning effect of the product is due to the presence of the nonionic organic detergent and the mixed water-soluble inorganic and zeolite detergent materials. While the product has a satisfactory cleaning effect, it also contains sufficient plasticizer, which is substantial on the laundry so that the finished laundry is noticeably softer and more statically free than laundry washed with control compositions that do not contain such a plasticizer. Normally it would be expected that comparatively high concentrations of nonionic detergents and plasticizers, which themselves are usually liquid, pasty, semi-solid or waxy, would cause the product to become "dull" or poorly sprinkling with a tendency to collapse during storage, but depending on the application of the nonionic detergent to the base particles in liquid form and its penetration into the interior of these particles, with only a relatively thin coating thereof on their surfaces, which is then coated with zeolite powder (and sometimes some plasticizer powder), a very free-flowing product that does not bake itself together. The preferred mixture of carbonate and bicarbonate in the base granules forms a highly desirable base for sorption of the nonionic detergent and provides sufficient detergent builder material or provides pH adjusting effects to make the product a satisfactory detergent.

However, other base materials can also be used provided that they are sorptive in a similar manner, e.g. spray dried pentasodium tripolyphosphate, sodium carbonate. When the bicarbonate is included, it lowers the normally extremely high pH value that would otherwise be obtained by the use of carbonate alone and makes the product safer to use than a carbonate-enhanced detergent. It also significantly improves the ability of the composition to sorb nonionic detergent, especially when the bicarbonate is largely in the form of Wegscheider's salt. In addition to preventing the nonionic detergent from causing stickiness or poor dispersibility, the zeolite powders on the surfaces of the particles also protect the interior of the product from the effects of external moisture and humid conditions. The compositions can thus be marketed without the use of special wax-coated protective layers on the cartons. Due to the affinity of the zeolite for moisture, it absorbs this moisture before the moisture can penetrate into the interior of the particles, where the moisture could have a detrimental effect on the bicarbonate or carbonate or where it could, depending on the formation of moist alkaline environment, adversely affecting any of the other product ingredients, such as the plasticizer or any of the various additives or aids. The ion-exchanging zeolite, which is present on the outside of the particles and which acts quickly to remove calcium ion from the wash water, acts to remove any harmful calcium ions (and other hardness-forming ions) before they can react with any other components of the detergent plasticizer composition, such as additives , and before they can adversely react with the laundry or the dirt thereon, which reaction could cause the laundry to retain the dirt more effectively by the detergent. In addition, since the zeolites are intimately associated with the nonionic detergent, they are better kept in suspension by the nonionic detergent during the initial period of contact with the wash water, at which time they would normally be of a particle size significantly larger than their final particle size. more likely to be caught by the laundry textiles. Such a capture or containment would lead to remarks, as it could cause a lighter appearance of dark-colored laundry.

The nonionic detergent helps to keep the zeolite particles suspended until they break down into smaller particle sizes, which are not so prone to deposit on the wash. } The comparatively large particle sizes of the invented products and of the starting materials are somewhat unusual, but result in very free-flowing or easily dispersible particles which nevertheless dissolve rapidly and have a high bulk density. Due to the comparatively large particle sizes of the builder salt, better absorption of nonionic detergent is obtained while obtaining the desired coating effect, not remarkable formation of paste, and the surfaces of the particles contain sufficient nonionic detergent to retain the desired coating of zeolite powder.

By keeping the plasticizer in the interior of the product, such as when it is added to the base particles as a liquid before application. '' KTTTT T TFK "-_- ~. * Ut-Å f -, _._ ^ afriinil '7713167-0 24 the zeolite or when it is present in a particle to be coated later, initial contact between the plasticizer and the wash is prevented, which is desirable as the fabric softening compound would otherwise deposit on the fabrics and a reaction between the plasticizer would also occur. and the dirt on the laundry or the laundry tissue itself, which would interfere with the cleaning of the laundry.In some cases when "external" plasticizer is added to the laundry and begins to melt, it forms greasy stains on the laundry which inhibit cleaning at the sites of these stains. The invention helps to prevent such undesirable staining by first contacting the zeolite and at least some of the nonionic detergent with the laundry. Additives or aids are retained in the interior of the invented particles in a similar manner their initial contact with the laundry is prevented, which is often desirable. Thus, in the case of fluorescent whitening materials, such as those of the stilbene whitening type, first contacts between whitening particles and the laundry are prevented by the incorporation of the whitening in the interior of the particles, thereby preventing extensive whitening stains on the laundry. The following examples illustrate a variety of embodiments of the invention, but the invention should not be construed as limited to these examples. Unless otherwise stated, all parts are by weight and all temperatures are expressed in OC. Example 1 Percentage Mixed sodium carbonate-sodium bicarbonate as builder salt particles (Snowlite I, about 1: 2 as weight ratio of Na 2 CO 3 to NaHCO 3, with particle sizes in the range 0.149 - 0.84 mm) 27.8 Neodol 25-7 (nonionic detergent condensation product of a C1-25 higher-fat alcohol with an average of 7 moles of ethylene oxide, manufactured by Shell Chemical Company) 18.5 Type 4A crystalline zeolite with high ion exchange capacity (Zeolite CH-252-91-1) , with particle sizes in the range of 0.053 - 0.088 mm, with final particle sizes in the range of 3 - 7 microns, averaging about 5.2 microns, manufactured by JM Huber Corp.) 46.3 Distearyl dimethylammonium chloride (Arosurf TA-100, 95% active ingredient in powder form with 7 particle sizes in the range of about 0.095 - 0.177 mm (160 - 80 mesh), manufactured by Ashland Chemical Company) 7.4 The carbonate-bicarbonate detergent granules are charged at room temperature (at 250 ° C) to a lutand e drum with 80 inclination, which rotates at a speed of about 40 rpm, and for a period of 5 minutes the nonionic detergent is sprayed, at 300 ° C, on the moving surfaces of the particles, after which mixing in the drum is continued for a further 5 minutes, after which time zeolite powder- <._. .___. .... .___ ._ _ _.-. _ .__._._ ._ __ _____ ,, ____, _______, _, 7v1s167 ~ o 26 year is mixed with the product, also for a further 5 minute period. The spray of the nonionic detergent is in the form of droplets which are largely in the diameter range 0.149 - 0.297 mm and during the spraying and subsequent mixing the particle sizes of the contents of the mixture increase slightly and some finer particles included are agglomerated 7 to within the range 0.149 - 0.84 mm. The zeolite addition is carried out for a period of about 5 minutes (times of 1 - 10 minutes are typical) and at the end of this time the particles of this intermediate product are globular with sizes in the range 0.42 - 4.76 mm.

In the next step, the powdered fabric softener is mixed with the detergent salt nonionic detergent zeolite intermediate and mixing is continued for a period of 8 minutes, during which time the plasticizer particles adhere or stick to the larger particles. The resulting product has an unpackaged bulk density of about 0.8 g / cm 3 and is free-flowing. It is packaged and stored and does not prove to cause any significant_baking or cake formation during storage under normal storage conditions during normal storage times.

When such a stored package is opened, the detergent plasticizer composition flows out easily and the bulk density of the composition is about 0.8 g / cm 3. When subjected to actual washing tests or practical washing tests, the product obtained is found to be non-dusting, free-flowing, non-caking and has acceptable cleaning effect and emollient properties for commercial applications, compared to favorable tripolyphosphate-reinforced detergents. plasticizer compositions of a similar active ingredient content. The zeolite does not deposit remarkably on the laundry and does not lighten the colors of dark colored laundry garments and the carbonate has no harmful effects on the cotton, polyester and acrylic material that is washed, due to the presence of the bicarbonate, which results in the washing water having a pH value of about 9.8. No noticeable float stains are formed on the wash either by compounding with plasticizer on the laundry, apparently due to the fact that the plasticizer is largely protected from initial total contact with the wash by the zeolite on the particle. - the surfaces.

In a comparative experiment, finely divided powders of sodium carbonate and sodium bicarbonate with particle sizes in the range 0.053 - 0.88 mm are used and these are agglomerated to a particle size in the range 0.149 - 0.84 mm by preliminary treatment with 5% by weight of a 20% aqueous solution of cereal starch paste sprayed on the moving particles of the powdered carbonate and bicarbonate in the same mixing drum as previously described, for a period of about 3 minutes, the drum moving at low speed, t. ex. 10 rpm. The resulting product is a useful detergent plasticizer composition of the same concentration as used in the previous experiment (1/4 - 1/2 cup or about 45-90 g per 65 liters of wash water), while washing batches of about 4 kg of soiled laundry. but it is not as free-flowing as the previously described detergent plasticizer composition. When only sodium bicarbonate is used as the initial builder salt, the product does not wash as well as the described preferred product and when carbonate alone is used, the product is more alkaline than desirable and is not as free-flowing. However, the carbonate-containing composition can be used as a detergent plasticizer composition in applications where higher pH values can be tolerated, although in the ordinary market it will not be as acceptable as the preferred products of the present invention, due to its comparability. poor spreading properties and higher pH value.

In a modification of the above examples, the particles of Arosurf are fusion agglomerated to sizes in the range of 4.76 - 0.42 mm before being added to the rest of the composition. Due to similar particle sizes, no segregation of plasticizer is obtained from the previously produced rounded grains, but in some cases easy "floating" on washed laundry can be observed, ----. ~ _..._ _ ... _ .., ......, __.......__........._..___ ,. _, _ ,, _ l ...____. . f, ._ d- _ .. m. ._. _ .. = :: ¿; 7713167-o 28 although such results are generally not considered serious enough to provoke complaints from the average consumer.

In another modification of the example, the plasticizer is melted together with the nonionic detergent and sprayed onto the base grains to be absorbed into the inner portions thereof and so that a smaller portion enters the surfaces of these grains before being coated with zeolite particles. The product produced has the same desirable high bulk density and particle sizes as previously described and constitutes an effective detergent plasticizer product in which the plasticizer is protected from initial contact with the laundry, thereby avoiding desirable staining.

Similar results are obtained when the molten plasticizer in the form of quaternary ammonium halide is sprayed on the tumbling base particles followed by spraying of nonionic detergent and "dusting" the zeolite powder on the particles. In this latter embodiment, style-type fluorescent bleach (Tinopal SBM), mixed with Tinopal ÉBS (0.5% and 0.05%, respectively) is mixed with the zeolite before being applied to the non-ionic detergent-coated granules. The fluorescent bleach is thus effectively prevented from coming into substantial contact with the quaternary ammonium compound and any adverse reactions between the two compounds are inhibited. When this product is used to wash laundry, the fluorescent bleach and the nonionic detergent are both actively active in the wash water before potentially interfering plasticizers are released from the particles.

In other modifications of the process, a quaternary ammonium compound is sprayed in liquid form on the surfaces of the zeolite particles before these particles are coated on the nonionic detergent coated and carbonate and bicarbonate mixture.

The resulting product is comparable to the properties mentioned earlier. This is also the case when the powdered quaternary near the ammonium compound of the particle size mentioned above is mixed with the zeolite and this mixture is coated on the waxy-like, fatty surface of the non-ionic detergent coated base particles. In yet another approach, the powdered quaternary compound is adhered to the nonionic detergent coating on the core particles and the zeolite powder is coated over it. Thus, a useful detergent plasticizer composition having the properties previously described is obtained.

Example 2 Percent Snowlite I 19 BritesiJ.CQ aqueous silicate particles (18% H 2 O, Na 2 O: SiO 2 ratio = 1: 2, manufactured by Philadelphia Quartz Company) 9 Neodol 25-7 "14 Zeolite type 4A (Zeolite CH-252-91 -1) 50 Distearyl dimethylammonium chloride (Arosurf TA-100) The snowlite particles are charged at room temperature to the inclined drum according to Example 1, which rotates at 12 rpm. The aqueous silicate, which is suitably about the same particle size, is added. to the drum for a period of about 2 minutes while mixing, and mixing is continued for another 3 minutes to mix the silicate uniformly with the carbonate bicarbonate particles. For a further period of 5 minutes, the nonionic detergent is sprayed, at a temperature of about 500 DEG C., mixed with the plasticizer, on the moving surfaces of the particles, which are preheated to 40 DEG C. The procedure from this point onwards is the same as in Example 1. The resulting product is an excellently concentrated high-performance or strong phosphate-free detergent plasticizer composition which is useful for washing laundry at a concentration of 0.1 - 0.2% in the washing water (0.5% is most often used in top-loading washing machines). ).

The product has a bulk density of about 0.7 - 0.8 g / cm3 and is free-flowing after normal storage without the use of a carton with a protective layer. The aqueous silicate helps to increase the detergency effects of the detergent and improves its anti-corrosion effect, compared with the products of Example 1, although those products are also satisfactory in both respects.

Example 3 Percent Snowlite I 27 Neoaol 25-7 å v 19 Neodol 25-3A (sodium polyethoxy-higher-fat alcohol sulphate (C12-25 alcohol and 3 moles of ethylene oxide per mole), 60 '% active ingredient, 25% H2O and 15 % C2H5OH, manufactured by Shell Chemical Company) 4 Zeolite of type 4A (Zeolite CH-252-91-1) 40 A Distearyldimethylammonium chloride 7 'The preparation procedure of Example 1 is followed where appropriate, except that Neodol 25-3S mixed with Neodol 25-7 and both are sprayed on the Snowlite particles together. The resulting product is an excellent strong detergent plasticizer composition, free-flowing, non-sticky, non-lump-forming during storage and has a desirable high bulk density (0.6 - 0.8 g / cm 3).

Due to the content of additional anionic detergent, this product is slightly better as a detergent than that of Example 1. No remarkable disturbances between the anionic and cationic materials included are obtained during storage, due to the segregation of the two types of materials and particles. At a mo-. _.> ...__._._..., __.-__...._._.._ .. f -__.._._._._.._...__ .. "-. - _ ._ ._.__._-_._._._-. ...____., ____ __ __, __. 7713167-'0 31 defining the procedure according to the example is added to the cationic the plasticizer to the base particles together with the nonionic detergent and the anionic detergent is mixed with zeolite and added to the mainly nonionic detergent coated particles.On another modification, Neodol 25-3S is first added together with a portion of Neodol 25-7 to the carbonate-bicarbonate particles and additional nonionic detergent is then added as a coating for these particles to isolate the anionic detergent from the later added quaternary ammonium compound.In yet another modification of this experiment 0.5% replaces Tinopal 5BM as a fluorescent bleach a similar percentage of Neodol 25-3S and mixed with the Snowlite material before applying Neodol 25-7 and Neodol 25-3S to the mixture. derived from the later applied quaternary ammonium compound. All of these products have the desired particle sizes, bulk densities and other product characteristics previously indicated.

Example 4 This example describes a further modification of the products and methods of the present invention, where additional quantities of nonionic detergent can be incorporated into the product by utilizing successive coating techniques. In Examples 1-3 above, the liquid nonionic detergent is applied in a sufficient amount to penetrate into the inner portions of the Snowlite particles or other base particles, such an excess being present that it wets the surfaces of the particles so that this excess causes the zeolite powder to adhere to the surfaces. In some cases when it is desired to use more nonionic detergent in the product, which gives a more concentrated detergent composition, and the procedures of Examples 1-3 are followed, causing and promoting the excess liquid to form an agglomerate or a paste. By the process of this example such an undesirable result is avoided and additional non-ionic detergent is satisfactorily incorporated into the product, which is still free-flowing and has a high bulk density. By this process, the particle size can also increased in a desirable manner.

The procedures of Examples 1-3 are followed, but in each case, based on 100 parts of the product resulting from the use of the methods of these examples, an additional five parts of nonionic detergent is sprayed onto the product and a further 10 parts of zeolite is then mixed into the product to adhere to the nonionic detergent coating thereon (using the spraying and mixing procedures described in Examples 1-3). The particle size increases by about 5% (diameter), but the product is still of about the same bulk density as previously obtained and is still free-flowing and non-shrinking. In further experiments, an additional 5 parts of the nonionic detergent is sprayed on the two-step product and an additional 10 parts of a zeolite is dusted on this product, obtaining similar desirable results (using the same spraying and mixing methods. ).

In performing the successive enriching coating operations described, the Snowlite particles or other base particles and the quaternary ammonium compound are not usually reapplied, but this can be done when it is advantageous.

Normally, as many as 6 transfer operations can be used, but it is preferred that a limitation be made to 3 such operations, as is the case with the "further experiment" described above. It is also preferred that the total amounts of nonionic detergent and zeolite in the coating or coating operations following the first operation should be limited to the amounts used in the first operation and is preferably limited to half of these amounts, with the pro- the portions of the nonionic detergent and the zeolite are within the proportions of the aforementioned percentage ranges.

N ul .r 1 »ana-nen; .-, y I-'v .rage __., -;:, 1.., .., _. Example 5 The procedures of Examples 1 - 4 are repeated, using Snowlite II instead of Snowlite I, crystalline zeolites of types X and Y with similar particle sizes and amorphous zeolites were used instead of zeolite of type 4A and The Neodol materials 23-6.5 and 45-11 and the Alfonic materials 1618-65 and 1412-60 were used instead of Neodol 25-7 and Aliquats H226 and Aliquats 400, Arquad 2HT-100, Culversoft WS paste and Varisoft 100 was used in place of the Arosurf TA-100 to obtain comparable high flow density free flow detergent plasticizer compositions. The only changes in the manufacturing technique are in maintaining the temperature of the nonionic detergent high enough to ensure that it is in a liquid state when sprayed on the surfaces of the base particles.

The proportions of the various components are also modified 110% and 130%, while being kept within the percentage and proportion ranges previously mentioned. Care is taken that the proportion of nonionic detergent used is such that a non-absorbed portion is provided on the surface of the base grains in the form of an adhesive coating to retain the zeolite particles. When the nonionic detergent is normally solid, the temperature of the detergent is kept high enough at the time of application of the zeolite so that the zeolite particles will adhere to the nonionic detergent and the base particles. When the cationic plasticizer is likewise a solid material and is to be applied to the interior of the base particles, the temperature of this agent is raised high enough so that it becomes liquid for such an application, either alone or together with a nonionic detergent.

The particularly desirable results obtained in the above examples and in the following procedures of the present invention for preparing the compositions thereof are unexpected. Although the use of mixed sodium carbonate-bicarbonate products (each particle comprises such a mixture) of the type described in ........._....... .__....-_.... ......_.._._.___ ..,. , _, _ .__ .- ~. ~ ._-__. U.S. Pat. No. 77,136,166 and 34 are disclosed in U.S. Pat. No. 3,944,500 as propellants for nonionic detergents, there was no indication that high bulk density products similar to those of the present invention could be used as core or base particles. Wegscheider's salt-carbonate-bicarbonate material, which often also includes sesquicarbonate, is in fact described as having a low bulk density (the range is about 0.4 - 0.5 g / cm 3).

In the present case, although 0.6 g / cm 3 is considered to be a high bulk density (packed) for detergent plasticizer products, the products prepared in accordance with the present invention generally have even higher densities, which are normally about 0.7 g. / cm3 or higher. The presence of the zeolite particles and their retention at the base particles is not described in the literature, nor is there any idea of using sufficient liquid nonionic detergent to maintain a coating or coating thereof on the base particles, despite the high sorption of liquid by such particles. Nor has the incorporation of a cationic plasticizer into such compositions in the various ways described and its protection from reactive materials in the composition and from initial contact with the laundry being washed been described or suggested in the known literature. The process of the present invention provides a non-segregating, free-flowing product with a desired comparatively large particle size and which contains even more nonionic detergent than the base particles can normally hold.

During the application of the nonionic detergent to the core or base particles, which absorb much of the nonionic detergent, the "excess" of nonionic detergent forms a coating or coating on the surfaces of the particles which is of a greasy or waxy appearance and the particles does not agglomerate in any remarkable way, but retains the smaller zeolite particles that are later applied. The mixture before the addition of the zeolite is not pasty, rather similar to the moist sand where each particle is kept in an unattached relation to other such particles or is kept soluble. The final products obtained are free-flowing, despite the presence of 10 - 100% of Wegscheider's salt in the form of needles in the base materials, partly due to the coating of more finely divided zeolite helping to round them or make the particles spherical. . In addition, the relative sites of the various components in the product grains are desirably functional and the buffering action of the base particles, when carbonate-bicarbonate is used, is advantageous in the washing (pH value of a 0.1% aqueous solution of Snow1ite). the material is about 9.8).

It is considered important that the particles of the * finished product are within the range of comparatively large sizes provided, but when in the above example the conditions change (usually by using smaller base particles) so that smaller particles are obtained, t .ex. those in the range of 0.149 - 2.38 mm, higher bulk densities are achieved than for the usual detergent plasticizer products, and the products produced are useful in a variety of applications for detergent plasticizer compositions, although they are not as free-flowing or sprinkling or appealing as the preferred embodiments of the present invention.

The invention has been described with reference to a number of embodiments and illustrative examples thereof, but it is not to be limited thereto as it will be apparent to those skilled in the art that after having read the foregoing description, they will be able to use replacement materials and equivalent materials without departing from the invention. the concept of the invention.or the scope of the invention. 'men QUALnï

Claims (11)

_ mzâev-o i 36 P a t e n t k r a v- A free-flowing particulate detergent plasticizer composition prepared by an agglomeration process and having a bulk density of at least 0.6 g / cm 3 and particle sizes in the range of 0.42 - 4.76 mm, characterized in that it comprises core or base particles of an alkali metal scrubber salt selected from a group consisting of sodium carbonate mixed with sodium bicarbonate, sodium carbonate, sodium bicarbonate, pentasodium tripolyphosphate, tetrasodium pyrophosphate, sodium silicate and potassium particles, normally borax, borax, liquid or pasty nonionic detergent in the interior of these particles and on the surfaces thereof and coated with calcium ion exchange zeolite particles having a final particle diameter in the range of 0.005 - 20 μm adhering to the surfaces of the nonionic detergent detergent salt particles, and a waxing agent; which is located outside t on or inpm_ said particles, said zeolite having the following chemical formula: (Mzo) (Alzopy (siopz xw Hzo where M is sodium or potassium, y is 0.8 - 1.2, z is 1.5 - 3, 8 and W represent the water content of about 1.5 - 36% by weight of said zeolite, and the weight percent of said builder salt, said nonionic detergent, said zeolite and said plasticizer are in the range of 20 - 40%, 12 - 30%, 30 - 60% and 4 - 12% respectively. 2. A composition according to claim 1, characterized in that the detergent salt base particles comprise alkali metal carbonate and alkali metal bicarbonate in a weight ratio in the range 1:10 - 10: 1 and have particle sizes in the range 0.149 - 0.84 mm, that the zeolite is selected from a group consisting of crystalline, amorphous and mixed crystalline amorphous azeolites of types A, X and Y, that the nonionic detergent is a higher fatty alcohol-1 polyethylene oxide condensate wherein the higher fatty alcohol has 10 to 18 carbon atoms and the polyethylene oxide has 3 to 15 moles of ethylene oxide per mole of higher-fat alcohol, that the emollient quaternary ammonium compound is a normally solid quaternary ammonium halide in particulate form which adheres to the outer surface of the resulting particle. 3. characterized in that the alkali metal carbonate is sodium carbonate, that the composition according to claim 2, the alkali metal bicarbonate is sodium bicarbonate, that the mixture of sodium carbonate and sodium bicarbonate contains and that the weight ratio between in the range 1: 3 - 1: 1, that comprises Wegscheiders , Na2CO3 and NaHCO3 are type A with a final particle - 3 - 12 μm and a moisture content of 10 - 25%, that the nonionic detergent is a condensation product of a higher-fat alcohol with 10 - 18 carbon atoms and 6 - 12 moles of ethylene oxide per mole, that the soft zeolite is a zeolite of size in the range making the quaternary ammonium compound is a di-higher-alkyl-, di-lower-alkyl quaternary ammonium chloride and that the finished product has mainly spherical particles. 4. characterized in that the resulting particle is coated with a composition according to claim 1, a normally liquid or pasty nonionic detergent, which detergent is coated with ion-exchanging zeolite particles. 5. Composition according to claim 1, characterized in that the main part of the plasticizer is present in the interior of the detergent-salt-base particles. * iåoon QUALITY 7713167-0 6. A composition according to claim 1, characterized in that the emollient and the nonionic detergent are present within and on the surface of said detergent salt base particles. A process for the preparation of a free-flowing, particulate detergent plasticizer composition having a bulk density of at least 0.6 g / cm 3 and particle sizes in the range 0.42 - 4.76 mm according to claim 1, characterized in that a liquid nonionic detergent is mixed with builder salt base particles so that said detergent is absorbed into and coats said builder salt particles, b) mixing the product of step a) with zeolite particles, whereby the zeolite particles adhere to the surface of the resulting the particles, and c) mixing the product according to step b) with plasticizer particles having a size in the range 0.095 - 0.177 mm, whereby said plasticizer adheres to the surfaces of said zeolite coated particles. A method according to claim 7, characterized in that a) the plasticizer in liquid form is mixed with said detergent salt base particles so that the majority of the plasticizer is absorbed in said detergent salt particles, b) mixing the particles obtained in step a) with said nonionic detergent in liquid form, so that the detergent is absorbed in and coats said particles, and.-_.._. _ f _...._.._......_._ _,, ___... _.-..._ í ...____..____..____...._. f 3, 7713167- * 0 c) mixing the product according to step b) with said zeolite particles, whereby the zeolite particles adhere to the surface of the resulting particles. A method according to claim 7, characterized in that a) said plasticizer and said nonionic detergent are mixed together at a temperature sufficient to form a liquid mixture, b) mixing the liquid mixture according to step a) with the builder base particles, so that said liquid mixture is absorbed in and coating the builder salt particles, and c) mixing the product of step b) with said zeolite particles, whereby the zeolite particles adhere to the surface of the resulting particles. 10. A method according to any one of claims 7, 8 and 9, characterized in that the product obtained is coated with an additional nonionic detergent in liquid form and that this detergent coating is coated with additional zeolite particles with final particle diameters in the range 0.01 - 20 μm. A method according to claim 10, characterized in that the additional detergent is a normally liquid or pasty condensate of higher fatty alcohol and polyethylene oxide, wherein the higher fatty alcohol has 10-18 carbon atoms and the polyethylene oxide content is 3-15 moles of ethylene oxide per mole of higher fatty alcohol, and that the additional zeolite is selected from the group consisting of crystalline, amorphous and mixed crystalline and amorphous zeolites of type A, X and Y, and that the amounts of such nonionic detergent and zeolite applied afterwards do not exceed half of the total content of said nonionic detergent and said zeolite in said product. IN